KR100743079B1 - Method for dyeing of polyarylene-1,3,4-oxadiazole - Google Patents

Abstract

A dyeing method of the polyarylene-1,3,4-oxadiazole fibers is provided to prevent an environmental problem from generating by means of dye with cation. The fiber is dyed by the cation dyestuffs. The polyarylene-1,3,4-oxadiazole fiber has a shape such as the sliver, spinning yarn or fabric. The cation dyestuff is at least one selected from a group consisting of cationic yellow 5GL, cationic yellow 3GL, cationic yellow GN, cationic G/Yellow GL, cationic orange GL(C.I.Basic Orange 21), cationic Brill. Red 4G, cationic pink FG, cationic red RP, cationic red GT, cationic red 5B, cationic red 6B, cationic red GRL, cationic blue BG, cationic blue BRL, cationic blue GRL, cationic navy blue BL, cationic black GLL, cationic black GH, cationic black 2GH. The cation dyestuff of 20 to 30% owf(one the weight of fiber) is used to the polyarylene-1,3,4-oxadiazole fiber. The dyeing is performed under the acid atmosphere of pH 4 to 5.

Description

Method for dyeing polyarylene-1,3,4-oxadiazole fibers {METHOD FOR DYEING OF POLYARYLENE-1,3,4-OXADIAZOLE}

The present invention relates to a method for dyeing polyarylene-1,3,4-oxadiazole fibers, and more particularly, does not use an organic solvent and does not cause environmental problems, and can significantly improve dye adsorption. A method of dyeing polyarylene-1,3,4-oxadiazole fibers.

Flame retardant fibers such as wholly aromatic polyamide fibers and polyimide fibers have a dense fiber structure and are difficult to dye using dyes by conventional dyeing methods, and thus have difficulty in practical use.

Japanese Patent Laid-Open Publication No. Hei 5-331781 uses aramid fibers as methyl terephthalate, dimethyl isophthalate, dimethyl phthalate, and the like to dye a flame retardant material such as polyarylene-1,3,4-oxadiazole fiber. A method of dyeing at 130 ° C or 170 ° C is disclosed, and Japanese Patent Laid-Open No. Hei 10-001884 discloses a method of immersing in N-methyl-2-pyrrolidone for 7 days and then dyeing at 130 ° C for 60 minutes. .

However, when the organic solvent is used as described above, there is a problem that wastewater discharged during the dyeing process pollutes the environment.

On the other hand, Japanese Patent Laid-Open No. 2-299674 discloses a high temperature dyeing method for dyeing a polyetherimide fiber material at a temperature of 135 to 140 ° C by a method that does not use an organic solvent.

Japanese Laid-Open Patent Publication No. 63-256765 discloses a method of swelling aramid fibers under vacuum and dyeing them with a dye.

In order to solve the problems of the prior art as described above, the present invention does not use an organic solvent does not cause environmental problems, polyarylene-1,3,4-oxadiazole can significantly improve the dye adsorption rate It is an object to provide a method of dyeing fibers and polyarylene-1,3,4-oxadiazole fibers dyed by the method.

In order to achieve the above object, the present invention dyeing of polyarylene-1,3,4-oxadiazole fiber comprising the step of dyeing with cation dye (cation) Provide a method.

The present invention also provides polyarylene-1,3,4-oxadiazole fibers dyed by the above method.

Hereinafter, the present invention will be described in detail.

The present inventors have used a cationic dye to dye polyarylene-1,3,4-oxadiazole fibers, using a cationic dye, a disperse dye, an acid dye, and the like. It was confirmed that the dye adsorption power is the best, based on this, the present invention was completed.

The polyarylene-1,3,4-oxadiazole fibers of the present invention are dyed using a cation dye, and more specifically, at a temperature of 130 to 150 ° C. under an acidic atmosphere using a cation dye. It is characterized by staining for 1-2 hours.

The polyarylene-1,3,4-oxadiazole fibers used in the present invention are mainly used in fire clothing as a fiber material having self-flammability.

The polyarylene-1,3,4-oxadiazole fiber may be a conventional polyarylene-1,3,4-oxadiazole fiber, and may be used as fibers such as slivers, spun yarns, or fabrics. Any type of thing that can be made can be used.

The cation dye used in the present invention is a dye which has an amino group or an imino group and does not have a sulfonic acid group, and is water-soluble, and refers to a dye whose colored portion becomes cation in an aqueous solution.

The cationic dye may be categorized into a carbonium dye, a quinoneimine dye, an acridine dye, a thiazole dye, an azo dye, etc. in terms of chemical structure, and cationic yellow 5GL (CI) is commercially available. Basic Yellow 13), Cationic Yellow 3GL (CI Basic Yellow 11), Cationic Yellow 3GN (CI Basic Yellow 51), Cationic G / Yellow GL (CI Basic Yellow 28), Cationic Orange GL (CI Basic Orange 21), Cationic Orange GL (CI Basic Orange 21), Cationic Brill. Red 4G (C.I. Basic Red 14), Cationic Brill. Red 4G (CI Basic Red 14), Cationic Pink FG (CI Basic Red 13), Cationic Red RP, Cationic Red GT (CI Basic Red 18), Cationic Red 5B (CI Basic Violet 16), Cationic Red 6B (CI Basic Violet 7), Cationic Red GRL (CI Basic Red 46), Cationic Blue BG (CI Basic Blue 3), Cationic Blue FRL (CI Basic Blue 162), Cationic Blue GRL (CI Basic Blue 41), Cationic Navy Blue BL), Cationic Black GLL, Cationic Black GH, Cationic Black GH, or Cationic Black 2GH.

The cation dye is preferably used at 2 to 30% one the weight of fiber (owf) with respect to polyarylene-1,3,4-oxadiazole fibers, more preferably at 5% owf. will be. When the cation dye is used in less than 2% owf, there is a problem in that it is difficult to obtain a desired color due to its own color of the polyarylene-1,3,4-oxadiazole fiber, and when it exceeds 30% owf, color fastness There is a problem of degradation.

In the present invention, the dyeing of the polyarylene-1,3,4-oxadiazole fiber using a cation dye may be performed using a high pressure dyeing machine under an acidic atmosphere.

When the dyeing can be adjusted to an acidic atmosphere using a conventional acid solution, specifically pH is adjusted to 4 to 5, preferably pH 4.5. In this case, as the acid solution, a conventional acid solution which does not affect the dyeing of the polyarylene-1,3,4-oxadiazole fibers may be used. In particular, in the present invention, a 10% aqueous acetic acid solution may be used for an acidic atmosphere. use.

Such dyeing may be carried out in a conventional high pressure dyeing machine, in which case it is preferably carried out for 1 to 2 hours at a temperature of 130 to 150 ℃, preferably for 60 minutes at a temperature of 130 ℃.

In addition, the present invention may further use sodium nitrate (NaNO ₃ , sodium nitrate) when staining under the above conditions.

The sodium nitrate prevents decomposition of dyes that may occur when the dyeing of the present invention is carried out at a high temperature, and may be due to color stabilization.

The sodium nitrate is preferably used in an amount of 1 to 10% owf based on the polyarylene-1,3,4-oxadiazole fiber, and when the content is within the above range, it effectively prevents decomposition of the dye to effectively color. It can be stabilized even more.

In another aspect, the present invention provides a polyarylene-1,3,4-oxadiazole fiber dyed in the same manner as described above, wherein the polyarylene-1,3,4-oxadiazole fiber is a disperse dye or acid Compared with the case where the dye is used, the dyeing adsorption rate is excellent.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

2 g of polyarylene-1,3,4-oxadiazole fiber (POX) was immersed in a Triton X-100 0.1 g / L solution.

Cationic Golden Yellow GL (concentration 200%), Cationic Red GTL (concentration 200%), Cationic Navy Blue MRL (concentration 100%), and Cationic Black 3GRL (concentration 100%) The concentration was adjusted to 5% owf. At this time, the concentration of 200% Cationic Golden Yellow GL and Cationic Red GTL was used as 2.5% owf in terms of 100%. Then, to adjust the pH of the salt solution was added to a concentration of 2% owf of 10% aqueous solution of acetic acid and adjusted to pH 4.5. In addition, 10% owf of sodium nitrate (NaNO ₃ ) was added to prepare a liquid ratio. In this case, water was used as the solvent, and the liquid ratio was 1:20.

2 g of the infiltrated polyarylene-1,3,4-oxadiazole fibers were infiltrated into the prepared liquid ratio to start dyeing at 40 ° C., and heated up to 130 ° C. at a rate of 2 ° C./min. (130 ° C.) for 1 hour.

After the completion of the main salt, the dyed polyarylene-1,3,4-oxadiazole fibers were taken out and fresh dye was put into the balance to start dyeing the balance. Upon completion of the balance dyeing, the polyarylene-1,3,4-oxadiazole fiber was washed with cold water once and then dried.

Comparative Example 1

Instead of polyarylene-1,3,4-oxadiazole fibers in Example 1, 2 g of a white acryl cloth for dyeing fastness test using polyacryl fibers was used, and dyeing was started at 40 ° C. to 1 ° C. The same process as in Example 1 was carried out except that the temperature was raised to 100 ° C. at a rate of / min and maintained at this temperature for 1 hour.

Comparative Example 2

Two grams of polyarylene-1,3,4-oxadiazole fibers were soaked in a Triton X-100 0.1 g / L solution.

Foron Br., A disperse dye of Swiss Clariant. Yellow S-6GL, Foron Br. Red RD-BR, Foron Br. Blue S-G (concentration 400%) and Foron Black RD-3G (concentration 300%) were used to adjust the concentration to 5% owf, respectively. 2% owf of a dispersant (GW0386, Gauw Industries) was added thereto, the pH was adjusted to 4.5 using 10% aqueous acetic acid solution, and sodium nitrate was not used. At this time, Foron Br. Blue S-G and Foron Black RD-3G with a concentration of 300% were used as 1.25% owf and 1.67% owf in terms of 100%.

2 g of the infiltrated polyarylene-1,3,4-oxadiazole fibers were infiltrated into the prepared liquid ratio to start dyeing at 40 ° C., and heated up to 130 ° C. at a rate of 2 ° C./min. (130 ° C.) for 1 hour.

After the completion of the main salt, the dyed polyarylene-1,3,4-oxadiazole fibers were taken out and fresh dye was put into the balance to start dyeing the balance. Upon completion of the balance dyeing, the polyarylene-1,3,4-oxadiazole fiber was washed with cold water once and then dried.

Comparative Example 3

Except for using the polyarylene-1,3,4-oxadiazole fibers in Comparative Example 2 was carried out in the same manner as in Comparative Example 2 except for using a back polyester fabric for dyeing fastness test.

Comparative Example 4

Except for the cationic dye in Example 1 except for using the acid (Nylosan Yellow N-3RL, Nylosan Red N-2RBL, Nylosan Blue N-BLN, Nylosan Black FWL acid dyes of Swiss Clariant) It carried out by the same method as 1.

Comparative Example 5

In Comparative Example 4 was carried out in the same manner as in Comparative Example 4 except for using the white nylon cloth for dyeing fastness test in place of the polyarylene-1,3,4-oxadiazole fibers.

The K / S value was measured by Gretag Macbeth COLOR-EYE 3100 using each of the fibers dyed in Example 1 and Comparative Examples 1 to 5, and the sum of the K / S values of the main salts and residual salts of the dyed fibers for each dye was measured. The concentration was converted as a reference. At this time, the K / S value of the white cloth was subtracted from the K / S value of the main salt fiber and the residual salt fiber, respectively, and the two values were added as conversion standards. Values at wavelengths where the concentration of the main salt fiber was the maximum for each color are shown in Table 1 below.

In addition, the dyeing rate of each of the fibers dyed in Example 1 and Comparative Examples 1 to 5 was obtained, and the results are shown in Table 2 below.

As shown in Table 2, Example 1 dyed using a cation dye according to the present invention is more salt than when using a disperse dye or an acid dye for the polyarylene-1,3,4-oxadiazole fibers It could be confirmed that the yield rate is excellent. In addition, the dyeing rate of polyarylene-1,3,4-oxadiazole fibers was higher than that of polyacrylic dyes when dyed with cationic dyes. In particular, cationic black 3GRL was used. It was confirmed that the dyeing ratio of the polyarylene-1,3,4-oxadiazole fiber was about 12% higher than that of the polyacryl fiber.

These results indicate that dyeing polyarylene-1,3,4-oxadiazole fiber using a cation dye is superior to that of other fibers or dyes.

According to the present invention, by using a cation dye when dyeing polyarylene-1,3,4-oxadiazole fibers, there is no environmental problem due to the absence of an organic solvent, and a dispersion dye or an acid dye. In comparison, there is an effect of obtaining a significantly improved dye adsorption rate of 99.9% dyeing rate.

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, it is natural that such variations and modifications belong to the appended claims. .

Claims (8)

A method of dyeing polyarylene-1,3,4-oxadiazole fibers comprising the step of dyeing with a cation dye. The method of claim 1, Polyarylene-1,3,4-oxadiazole, characterized in that the polyarylene-1,3,4-oxadiazole fibers are in the form of slivers, spun yarns, or fabrics. , 3,4-oxadiazole) fiber dyeing method. The method of claim 1, The cationic dyes include Cationic Yellow 5GL (CI Basic Yellow 13), Cationic Yellow 3GL (CI Basic Yellow 11), Cationic Yellow 3GN (CI Basic Yellow 51), Cationic G / Yellow GL (CI Basic Yellow 28), Cationic Orange GL (CI Basic Orange 21), Cationic Orange GL (CI Basic Orange 21), Cationic Brill. Red 4G (C.I. Basic Red 14), Cationic Brill. Red 4G (CI Basic Red 14), Cationic Pink FG (CI Basic Red 13), Cationic Red RP, Cationic Red GT (CI Basic Red 18), Cationic Red 5B (CI Basic Violet 16), Cationic Red 6B (CI Basic Violet 7), Cationic Red GRL (CI Basic Red 46), Cationic Blue BG (CI Basic Blue 3), Cationic Blue FRL (CI Basic Blue 162), Cationic Blue GRL (CI Basic Blue 41), Cationic Navy Blue BL), Cationic Polyarylene-1,3,4-oxadiazole, which is at least one selected from the group consisting of Black GLL, Cationic Black GH, Cationic Black GH, and Cationic Black 2GH. oxadiazole) method of dyeing fibers. The method of claim 1, The polyarylene-1,3,4-, wherein the cation dye is used at 2 to 30% one the weight of fiber (OWF) relative to the polyarylene-1,3,4-oxadiazole fiber. Method for dyeing oxadiazole (polyarylene-1,3,4-oxadiazole) fibers. The method of claim 1, The dyeing method of the polyarylene-1,3,4-oxadiazole (polyarylene-1,3,4-oxadiazole) fibers, characterized in that the dyeing is carried out in an acidic atmosphere of pH 4 to 5. The method of claim 1, The dyeing method of the polyarylene-1,3,4-oxadiazole (polyarylene-1,3,4-oxadiazole) fibers, characterized in that the dyeing is carried out for 1 to 2 hours at a temperature of 130 to 150 ℃. The method of claim 1, Polyarylene-1,3,4, characterized in that 1-10% owf of sodium nitrate (NaNO ₃ , sodium nitrate) is further used for the polyarylene-1,3,4-oxadiazole fibers in the dyeing. -Method of dyeing oxadiazole (polyarylene-1,3,4-oxadiazole) fibers. A polyarylene-1,3,4-oxadiazole fiber dyed by the method of claim 1.